Process of preparing nitrogenous compounds.



L. L. SUM MERS.

PROCESS 0F PREPABING NITBOGENOUS COMPOUNDS.

APPLIUTIOI "LED FIDJI, 190B.

Patented Jan. 2, `1912.

2 .INRP-IEDM' l.

s fr( mwwuw Vwf' riff/)Wala H l 3 ATTURNISYS L. L. SUMMERS. 2806288 0I PBEPARINO NITROOENOUS COIPOUNDS.

uruonlol num rnmn. wou

1,013,460. Patented Jau. 2, 1912.

lll lll @QQV- i mlnn'nfmnnnmnnnnnunnnnrmnnnnnnnnnnn@i UNITED STATES Lm L. ulxm,

PATENT OFFICE.

CHICAGO. ILLINOIS.

' will 0f IBIPIING III'IIOGINOUI 0IPOUNDl 2b all whom it may concern:

Be it known that I, Lituano L. Sustituir,

a citizen of the United States2 residingat Chica o, Cook county Illinois, have in- 6 vent new 'and useful rocesses of .lnreparin Nitrogenous Compounds, of which the fo owing is a specification.

The object of my invention is to provide a new and useful process of pre aring nitrogenous compounds namely, t ose comunda of nitrogen anf elements auch as carn and hydrogen, or a combination of these, producing as a result ammonia having the chemical formula NIL, eyiinogen (LN, and

hydrocyanic acid Cim', from all of which may be obtained numerous salts and clieiui- .cel derivatives well known in the art.

. l have discovered that by the use of cold or refrigerated nitrogen or a coin ound of nitrogen, such as ammonia, using it preferably in a liquid state certain chemical reactions may be more readily brought about.

Referring to the accompanying drawings, Figure 1 is a lon itudinal sectional eleva- I' tion of an appara us for practicing in invention; Fig. 2 a similar sectional eevation of the fumace portion of the apparatus but on a larger scale than in Fig. l, and Fig. 3 a cross section on the line 3-3 of Fig. 2. 80 Before describa the details of my apparatas I will state t at no means or .devices are herein shown for liquefying the ainmonia or nitrogen inasmuch as auch device are now well-known in the arts. 'i6 Beferri to the particular apparatus illustrated m the drawings, the sinne consists essentially of a suitable furnace l, a retorty 2 I heated thereby and adapted to contain cer tain substances as hereinafter described. and a sup lyl pipe 3 for supplying the nitro'fenous iquid which is intrinlueeil in suitable manner by the instrumeutalities hereinafter described. This supply pipe 3, it will he uudashed, communicates with a source ot' ni-` I tx'ogonous liquid'which is either lifuid nit .obti'iined as hereinbefore descri wd. liq- -ni ammonia or other nitrogenous product. This liquid pipe 3 is provided a ong its length with a series of delivery pipes or injectorsentering the drum or retort. 2 at dif- 1 ferent points along the lenffth thereof but toward the front end tliereofl.a Each of these Inclination et Lettere Patent.

l'utent'cd Jun. 2, 1012. n. im. man in. nam.

:delivery pipes or injectors is provided with I an expansion valve 5 whereby the supply of the liquid nitrogen into the drinn or retort may lic accurately und niinutely controlled. l liy preference these vulves are arranged to he operated simultaneously and to this end the saine are operated by the single controlling rod 6' whose rotation in one direction or the other opens or closes said valves.

'llie drinn or retort V2 is arranged as shown at the upper portion of the furnace l, so that the furnace heats only the' lower portion of the drinn throu hout its entire length, the 'upper portion o the drum hein" provided with an insulating eovcrin 7,. he 'ends of the druiu are rovided wit i removable eovers 8 which wien the apparatus is in o ieration close the end openings thmagh w iich drum is rovided with a suitable stirrin or mixing evice such as theshaft 9 exten ing i longitudinally through the drinn or retort with hearings iii the covers 8 and having the series of arms 10 for stirring or agitating the is rotated in any suitable manner through power which may be4 a iled at one end, as the pulley 1l. l t wil understood that the covers 8 are provided with s\iitable.stiiif' ing hoxes 12 through which the shaft 9 passes. The products of coiiihnstion from the furnace, after coming into contact with the drum, are discharged into the flue 13.

In o .ration the drum or retort 2 is charges with a mixture of carbon in the toriii of charcoal or coke and an alkali metal l l--ueh iis-sodium the recise proportions being 5 immaterial though prefer to use an excess of curhon. Heut is su plied by the furnace i und the uniss iii the t ruin or retort is agitated h v the mixing or stirring device therein. When u suitable temperature is obf tained iu tlu charge, depending u ion the rei uctioii desired, the vulve control yingr rod (t l is operated and the valves .-'i are permitted l to discharge a suiall tuantitv of liquid anig iuoniu into the heater charge through the series of injectors 4. A sudden and violent. l reaction occurs, and various compounds of nitrogen, hydrogen and carbon result. There i is an instantaneous rise of pressure in thel is introduced the charge of carbon, hydrocarbon or various other substances. The' contents of the drum. This stirring device' drum or retort and a tendency for the gases formed to rush through the outlet pipe 14.

.-\ portion of the compound remains in the drum, being in a lixed con'ibinatiou with the highly heated carbon. The continual operation of the mixer insures an intimate contact between the injected material uml tlie alkali metal und carbon. The teni ieratiire iind the pressure in the driiiu 2 may regulated by the amount or frequency of the injections of the nitrogenous material, the. teilipcrature being lowered and the pressure being increased by increasing the amount or frequency of such injections. The gasilied portion of the contents of the drum 2 passes through the pipe or outlet 14 at the rearward end of thc drum to the absorbing vessels 15. The outlet 14 may be provided with a valve so that communication with the ab- A 30 sorbers can be shut off or a direct outlet may be maintained, as shown in Fig. t. The absorbing vessels may contain any standard reagents foret-he absorption of the gaseous products, but on account of the chemical atlinity of cyanogen compounds for minutely divided iron and also on account of the allinty of ammonia for sulfuric acid, the gases may he passed throu 'h an aqueous solution of ferrous sulfate, t ie product obtained being insoluble Prussian blue .from the cyanogen and soluble ammonia sulfate from the ammonia. 0r in the lirstabsorbing vessel, for instance, may begilaeed h droxid of otassiinn or sodium or the a $5 sorption o any hydrocyanic acid. The residual gases after assing through the' absorbers may be was ied to remove any traces of ammonia and the combustible products may be utilized in the ordinary manner as, 40 fq instance, providing heat to the furnace Villltier drum 2. In the present instance 1 have shown a series of three of these absorbing vessels, but. it will be understood that they may be of any desired number and of any suitable size and dimensions. These vessels communicate in series with each other, the lirst one thereof being connected with the outlet 14 of the drum by means of a pipe 17, while the vessels are arranged to communicate through suitable pipes 18.

These pipes extend into the receptive absorbing vessels to' a point near the. bottom thereof and below the line of material, that is the liiie of the reagents introduced therein for the purpose hereinbeiore stated. .When a high pressure results from the discharge. of the' lit uid uitrogenous material into the drum, it may be desirable to allow the liberatcd gases freeexit from the drum 00 through the outlet pipe 14, and the absorbing vessels would then be subiected lo the pressure in the drinn. In order to prevent anytendency of the solutions to be lifted ont of the a isorbing vessels, it is desirable to maintain them under pressure and tothis end I provide the outlet pi l0 lending NII,+Na=NaNII,4l-ll The .sodium amid in contact with the carbon will forin the sodium cyanid at about 700 or 800 C. in accordance with the equaf'on Na.Nllfl-C-:CNNa-t-HJ In this` reaction the fixed products in the drum will be sodium c 'anid and the volatile products will be h ro en. The proportion of material use in t e drum may vary within wide limits for an excess of either has no effect on the reaction other than upon the quantity of the products of the reaction.

lf the drinn be charged with`charcoal onlyI and tli'is heated to incandcscence, the reaction will take place in 'accordance with the equation The products therefore being volatile ammonium cyonid, and hydrogen, the fixed iortion remaining in the drum being caron. But if the action be continued until the carbon is largely utilized, the volatile products will also contain unspent ammonia as well as ammonium cyanid. These 'temperatures are well suited to the apparatus as shown. If, however, higher teiniratures be used and the apparatus be icated to a temperature of from 1,200 C to 1,500 C. mixtures of alkali metal salt-` or salts of alkaline earth metals and carbon may be utilized, and nitrogenous compounds may then be formed either from ammonia or directly from nitro en. Sodium is representative of the alka i metals whose compounds may be employed for this purpose and barium and magnesium are the alkaline earth metals. The part' ular compound employed ma be any o a considerable number, of w ich nitrate or hydrate will serve as suitable examples. The formation of the nitrogenous compounds from contact of nitrogen or ammonia with carbon, hydrocarbons and'salts of the alkali or alkaline earth metals may take place in accordance with various primary reactions from which compounds other compounds are foi-med in a secondary reaction. At atemperature of from 1,200 C. to 1,500 C. nitrogen may be caused to react with acetyanimee iene foi-med from hydrocarbons and hydros cyiinic acid will be produced in accordance carbonate or barium carbonate is used, caihon inonnxid will be formed through the reduction il the carbonate by theinciindescent cai-bon. Ammonia can be caused to react with the carbon inonoxid resulting in for- -iiiziiiiid in accordance with the equation eyanic acid and water in accordance with Vthe iii't. of bringing the equation HCONH,=HCN+H,O

Contact of the metallic salts and the highly heated carbon effects a reduction of the metal from the salts of the alkali or alkaline earth metals, which may be acted upon by nitro en or the nitrogcnous coinpound injccte( into the drum' 2. Thus metallic ma nesiuin forms a nitrid in accordance wit the equation 3Mg-{-2N=Mg,N2 which in the presence of water will form ammonia, thus Certain of the alkali or alkaline earth 'metals when reduced from their salts in the presence of incandescent carbon will forni a carbid. Thus barium reacts in accordance with the equation Hilft-20:13u()z and this carbid will react with nitrogen forming the cyanid, in accordance with the equation.

, For the purpose of securing a sutiiciently hi h temperature to reduce the alkali o r alcaline earth metals from their salts it will be convenient to use a diti'erent method of heating the drum 2 ecssive deterioration. This may readily be done by employing a resistor of any well known or approved tyie in the driim2. lhiis in Figs. 2.and 3 have shown, a longitudinally extending resistor 22 which niny be connected up in any -known manner to a y. source of suicient current to etlect the heatf ing of the drum. The .feature of my invention is not the particular means forvpro viding for the heating of the drum 2 or uieu'is for cooling the nitrogen 0r nitrogenous substance injected into the drinn 2, but in contact the highly hinted substances in the drinn 2 and the ling from the drum 2,

in order to avoid ex-v i'efrigei-.ated nitrogen er nitrogcnous compound in accordance with the above equations.

It is apparent that the process of forniin the nitrogenous compounds :nay be vari widely without exceeding the scope of my invention. Thus, in using an alkali metal such as sodium in contact with carbon in the drum 2, of Fig. 1, the tirst application of heat will cause the metallic sodium to melt at a temperature of about 05 C., and at a temperature of from 750 C. to 0001 C. the melted sodium vaporizes. As the cy-` yanida ilre formed at a temperature of from 750 C. to 850 C., it follows that in the ordinary processes there is a separation of the va'por of sodium from contact with the carbon. In injecting the refrigerated compound iiito the drum 2 the immediate lowering of the temperature in the drum causes a condensation of the sodium vapor and in the case of ammonia an intimate reaction between the sodium and the ammonia forming the amid. As the cooled amid is condensed in contact with the highly heated carbon the formation of the cyanid will take piace without an escape of the vapor 0f metallic sodium. In this particular rcaetion, excess ammonia and hydrogen would be the only volatile products escaping. the outlet 14 is closed until the action luis lbeen completed; the surplus of ammonia will be recovered in the absorber upon allowing the outlet 14 to communicate with the absorber. As ammonia is readily dccomposed at a temperature of from 600 C. to 700 C., the reactions taking place in the drum 2 can be controlled by controlling the temperature and by admitting a siiilicient -qiiantity of the gases to the druni 2, the teinperature ca n be lowered to a pointwhei'e any excess of ammonia will not be dccoiiiposed, but may ha caused to pass through the absorbers as combined nitrogen and hydrogen and thereby recovered, whereas, if the temperature of the drum is not lowered sutliciently to cause the nitrogen and hy drogen to recombine previous to dischargthey would pass through the solution in the absorbers, therahy wasting the nitrogen as an inert gas.

From the above reactions it will be a parent that part of the nitrogen maybecom ined with carbon or other fixed material and part may be coinhined in a gaseous state generally resulting in a union of nitro en and hydrogen, or nitrogen and carbon. y varving the fixed or incandescent element in t e retort or drum, various compounds may thus be obtained. As the gases formed are passed to the absorbing vessels and brought into intimate contact with various solutions, chemical combinations are ellected and prodf nets may be extracted for lise as hereinbcfore stated. By means of the apparatus and iinfois l[its terin earbonaceous material to refer to 'other form of carbon or a hydro-carbon.

der theprocess described cyaiiogen roducts, ammonia, amid and cyanamid p ucts are obtained, but'it will he understood that with a change of materials in the retort the nitrogen, carbon and hydrogen may be compounded with other products, the process bein general in its application fort e fixation o atmospheric nitrogen, the production of cyanogen, etc.

In certain of the iliiiins I have used the that portion of the charge of the drum which furnishes the carbon, whether it be coke,

1 claim:

1. The process of preparing nitro enpus compounds which consists in intr ucii into heated carbonaceoiis material liqiiefi gus containing nitrogen.

2. The procesa of preparing nitro cnous imiiipoiindii which consists iii intro( ucing into heated hydrocarbons liquefied nitrogen.

8.' The process of 'preparing nitro nous compounds which consists in intro( uciiig into heated earbonaceousinaterial retriger iited as containing nitrogen. 0

4. .'he process of preparing intro enpus compounds which consists in mtr ueing into heated hydrocarbons refrigerated nitrogen.

5. The process of preparing 'nitro cnous compounds which 'consists in intr ucin into heated carbonaccous material, mix with an alkali, a li ueficd nitrogcneous gas.

6. The process o preparing nitro nous eoii'ipoiinds which consists in int ucing into 'heated li drocarlions mixed with an alkali, a lique ed nitrogenous gas.

7. 'lhe process of preparing nitro nous compounds which consists in intr ucing into heated earbonaieous material, iiiixedg with au alkali, refri erated nitrogen. g 8. The process o preparing' nitro enousi compounds which consists in int ucing' into heated hydrocarbons, mixed with an; alkiili, refrigerated nitrogen.

9. The process of preparing nitro cnous? compounds which consists in intr ucing;

into carbonaceous material under high heat and pressure a liquefied nitrogenous gas.

10. 'Iho process of preparing nitro nous compounds which consists in intr ucin into hydrocarbons under high heat an pressure a liquefied nitrogcnous gas.

1l. The process of preparing nitro cnous 55 compounds which .consists in intr ucing into curlxinaceous material under high heat and pressure refrigerated nitrogen.

12. 'llic process of preparing nitro cnous compounds which consists in intr ucing into hydrwarhons iuider high heat and pres -aire rcfrigeraied nitrogen.

' 13. 'lhc process of preparing iiitro nous compounds which consists in intr( iicing into carbonaceous material under high heat -aiid pressure a liquefied nitrogenous gas, thc

degree of lient and ircssurc of the cnrlions heilig rc ulntd hv t e amount of thc nitrogeu or l qiicflcd n'ltrogenous gas introduced.

14. 'lhe process of preparing nitro cnous compounds which consists in intro( ucing into hydrocarbons under high heat and pressure a liquefied nitrogenous gaa, the de ree of heat and pressure of the hydrocar iis being regulated by the amount of the nitrogcii or liquefied nitrogenous gas introduced.

lo. The process of preparing nitro enous compounds which consists in intr ucing into carboiiaceous material under high heat and pressure a liquefied nitrogenous gas, the degree of heat and ressure of the-`carbons being regulated by i)he frequency of introduction of the nitro en or iqueiied nitrogcnous as introdu 16. he process of preparing nitro .nous compounds which consists in intr iicing into hydrocarbons under high heat and pressure a liquefied nitrogenous gas, the,degree of heat and pressure of the hydrocarbons being regulated by the frequency of introduction of the nitrogen or liquefied nitrogenous gas introduced.

LELAND L. SUMMERS. Witnesses:

S. E. Hiniirm, S. Buss. 

